Composition and article for reduced food adhesion

ABSTRACT

The invention relates to a composition and article for reducing food deposit adhesion to cookware. More specifically this invention relates to a resin composition comprising a polysulfone or polyethersulfone resin having a glass transition temperature of at least 180° C., a fluorinated polyolefin, and an anionic surfactant. The invention also relates to an article comprising the composition.

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application is a division of U.S. application Ser. No.09/598,184 filed Jun. 21, 2000 and incorporated herein by reference,which is a division of U.S. application Ser. No. 09/300,861 filed Apr.28, 1999 and incorporated herein by reference.

FEDERALLY SPONSORED RESEARCH

[0002] Not applicable.

BACKGROUND OF THE INVENTION

[0003] 1. Field of the Invention

[0004] The invention relates to compositions and methods for reducingfood deposit adhesion to cookware. More specifically this inventionrelates to a resin composition having a glass transition temperature ofat least 180° C. containing an amount of at least one fluorinatedcompound effective to reduce food deposit adhesion on cookware made fromthe composition. The resin composition may optionally contain at leastone fatty acid ester, fatty acid amide, anionic surfactant, or a mixturecontaining at least one of the foregoing. The invention also relates toa method for providing plastic cookware having reduced food depositadhesion.

[0005] 2. Brief Description of the Related Art

[0006] Plastic cookware has gained increased acceptance and use inrecent years due in part to their relatively low cost, durability withlight weight, and flexibility in design. Unfortunately, adhesion of fooddeposits and the accompanying stains as observed with more traditionalmetal cookware is also obtained with plastic cookware. Non-stickcookware has been developed as a solution to adhesion of food depositsto reduce sticking and ease cleaning.

[0007] Methods to prepare non-stick cookware generally involveapplication of a surface treatment or lamination of a thin non-sticklayer to the surface of the cookware. These methods are expensive andreduce the cycle time of the manufacturing process. What is needed inthe art is a method for reducing the adhesion of food deposits onplastic cookware without secondary steps.

SUMMARY OF THE INVENTION

[0008] The method of the present invention to reduce adhesion of fooddeposits on cookware comprises a resin with a glass transitiontemperature of at least 180° C. and an amount of at least onefluorinated compound effective to reduce food deposit adhesion oncookware made from the composition. The resin composition may optionallycontain at least one fatty acid ester, fatty acid amide, anionicsurfactant, or a mixture containing at least one of the foregoing. Theinvention also includes the compositions and articles made from thecompositions having reduced adhesion of food deposits. Various featuresand advantages of the present invention will be appreciated andunderstood by those skilled in the art from the following detaileddescription.

DETAILED DESCRIPTION OF THE INVENTION

[0009] According to this invention, there is a method provided to reduceadhesion to food deposit on cookware made from at least one resin havinga glass transition temperature of at least 180° C. The need for the highglass transition temperature is to allow for the high temperaturescommon during food preparation. Accordingly, the resins have to havesufficient heat resistance to resist deformation during use. Suitableresins include polycarbonates, polyimides, polyamides, polyamideimides,polysulfones such as polyarylsulfones, including polyphenylsulphones,polyethersulfones, polyetherketones, polyetheretherketones, aromaticcopolyesters, and polyetherimides as well as various blends containingat least one of the foregoing resins. These resins are generally knownin the art as are methods for the preparation.

[0010] In one embodiment, the resin is a polyetherimide resin comprisingstructural units of the formula (I):

[0011] wherein the divalent T moiety bridges the 3,3′, 3,4′, 4,3′, or4,4′ positions of the aryl rings of the respective aryl imide moietiesof formula (I); T is —O— or a group of the formula —O-Z-O—; Z is adivalent radical selected from the group consisting of formulae (II):

[0012] wherein X is a member selected from the group consisting ofdivalent radicals of the formulae (III):

[0013] wherein y is an integer from 1 to about 5, and q is 0 or 1; R isa divalent organic radical selected from the group consisting of: (a)aromatic hydrocarbon radicals having from 6 to about 20 carbon atoms andhalogenated derivatives thereof, (b) alkylene radicals having from 2 toabout 20 carbon atoms, (c) cycloalkylene radicals having from 3 to about20 carbon atoms, and (d) divalent radicals of the formula (IV):

[0014] where Q is a member selected from the group consisting offormulae (V):

[0015] where y′ is an integer from about 1 to about 5. A particularlypreferred polyetherimide resin is the reaction product formed by meltpolymerization of 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propanedianhydride with one or more of paraphenylene diamine and metaphenylenediamine. The resins are commercially available from GE Plastics underthe mark ULTEM resins.

[0016] Other particularly useful resins include polysulfones havingrepeating units of the formulae (VI), (VI), (VIII), (IX), and (X):

[0017] . These materials are commercially available from BASF, Amoco,and ICI under a variety of tradenames.

[0018] Other particularly useful resins include polyamideimides of theformulae (XI), (XII), and (XIII) wherein n is an integer greater thanabout 20, preferably greater than about 50:

[0019] Typical commercially available polyamideimides are sold under thetrademark TORLON by Amoco Performance Products.

[0020] Other particularly useful resins include polyetherketones of theformulae (XIV), (XV), and (XVI) wherein n is an integer greater thanabout 20, preferably greater than about 50:

[0021] Typical commercially available polyetherketones are sold underthe trademarks VICTREX and ULTRAPEK by BASF.

[0022] A second key component of the present invention is an amount ofat least one fluorinated compound. The fluorinated compound preferablyincludes at least one fluorinated polyolefin or fluorinated siloxane orfluorinated siloxane polymer. The fluorinated polyolefins generally havean essentially crystalline structure and preferably have a melting pointin excess of about 120° C. The fluorinated polyolefins are preferably apolymer of one or more fluorinated monomers containing ethylenicunsaturation and optionally one or more other compounds containingethylenic unsaturation. The fluorinated monomer may be a perfluorinatedmonoolefin, for example hexafluoropropylene or tetrafluoroethylene, or apartially fluorinated monoolefin which may contain other substituents,e.g., chlorine or perfluoroalkoxy, for example vinylidene fluoride,chlorotrifluoroethylene and perfluoroalkyl vinyl ethers in which thealkyl group contains up to six carbon atoms, e.g., perfluoro (methylvinyl ether). The monoolefin is preferably a straight or branched chaincompound having a terminal ethylenic double bond and containing lessthan six carbon atoms, especially two or three carbon atoms. When unitsderived from monomers other than fluorine-containing monomers arepresent, the amount thereof is preferably less than 30 mole %, generallyless than 15 mole %. Such other monomers include, for example, olefinscontaining less than six carbon atoms and having a terminal ethylenicdouble bond, especially ethylene and propylene. Suitable fluorinatedolefins include fluorinated polyethylenes comprising repeating units ofthe structural formula (XVII):

[0023] wherein b is an integer in excess of 50 and Y¹ to Y⁴, which maybe the same or different, are selected from the group consisting ofhydrogen, chlorine, bromine and fluorine, with the proviso that at leastone of Y¹ to Y⁴ is fluorine. Preferred fluorinated polyethylenes for thepurposes of the present invention include poly(vinyl fluoride),poly(vinylidene fluoride), polytrifluoroethylene,polychlorotrifluoroethylene, polybromotrifluoroethylene,polytetrafluoroethylene, and copolymers thereof. A particularlypreferred fluorinated polyethylene is polytetrafluoroethylene. Othersuitable fluorinated polyolefins include polyperfluoropropane,perfluorobutadiene and polyhexafluoropropylene.

[0024] More specifically, polytetrafluoroethylenes are fully fluorinatedpolyethylenes of the basic chemical formula (—CF₂—CF₂—)_(n) thatcontains about 76% by weight fluorine. These polymers are highlycrystalline and have a crystalline melting point of over 300° C.Commercial polytetrafluoroethylenes are available from E. I. duPont deNemours & Co., Inc. under the tradename Teflon and from ImperialChemical Industries under the tradename Fluon.Polychlorotrifluoroethylene and polybromotrifluoroethylene are alsoavailable in high molecular weights and can be employed in blends of theinstant invention. Other preferred fluorinated polyethylenes arehomopolymers and copolymers of vinylidene fluoride. Poly(vinylidenefluoride) homopolymers are the partially fluorinated polymers of thechemical formula (—CH₂—CF₂—)_(n). These polymers are tough linearpolymers with a crystalline melting point at 170° C. Commercialhomopolymer is available from Pennwalt Chemicals Corporation under thetradename Kynar. The term “poly(vinylidene fluoride)” as used hereinrefers not only to the normally solid homopolymers of vinylidenefluoride, but also to the normally solid copolymers of vinylidenefluoride containing at least 50 mole percent of polymerized vinylidenefluoride units, preferably at least about 70 mole percent vinylidenefluoride and more preferably at least about 90% vinylidene fluorideunits. Suitable comonomers are halogenated olefins containing up to 4carbon atoms, for example, dichlorodifluoroethylene, vinyl fluoride,vinyl chloride, vinylidene chloride, perfluoropropene,perfluorobutadiene, chlorotrifluoroethylene, trichloroethylene,tetrafluoroethylene and the like. Commercially available fluorinatedpolyolefins of this class include copolymers of vinylidene fluoride andhexafluoropropylene such as Viton A, Viton A35 and Viton AHV sold by E.I. du Pont; copolymers of vinylidene fluoride, hexafluoropropylene andtetrafluoroethylene such as Viton B and Viton B50 sold by E. I. du Pont;copolymers of vinylidene fluoride, hexafluoropropylene andtetrafluoroethylene such as Dynamar sold by Dyneon; and copolymers ofvinylidene fluoride and chlorotrifluoroethylene such as Kel-F sold byMinnesota Mining and Manufacturing Co. Additional examples of preferablefluororesins include a copolymer of tetrafluoroethylene andhexafluoropropylene represented by the following formula (XVIII):

[0025] Among typical resins of this type, there are “Teflon FEP-J”(produced by Mitsui Fluorochemical) and “Neoflon FEP” (produced byDaikin Kogyo).

[0026] The fluorinated siloxanes and related fluorinated siloxanepolymers (collectively referred to herein as “fluorinated siloxanecompounds”) useful in the present invention include fluorinatedsiloxanes and related fluorinated polymers having mono-, oligo-, orperfluorinated alkyl group having one to about nine carbon atoms or amono-, oligo-, or perfluorinated aryl group. Usefulfluoroalkyl-functional organosilanes, or polymeric derivatives thereof,include those of the formula:

R¹—Y—(CH₂)₂Si(R²)_(x)(OR)_(3-x),

[0027] wherein R¹ is a mono-, oligo- or perfluorinated alkyl grouphaving one to about nine carbon atoms or a mono-, oligo- orperfluorinated aryl group, Y is a CF₂, CH₂, O, or S group, R² is alinear, branched or cyclic alkyl group having one to about eight carbonatoms or an aryl group and R is a linear, branched or cyclic alkyl grouphaving one to about eight carbon atoms or an aryl group and x is between0 and about 1. Specific examples include:tridecafluoro-1,1,2,2-tetrahydrooctyl-1-trimethoxysilane,tridecafluoro-1,1,2,2-tetrahydrooctyl-1-triethoxysilane,3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyltriethoxysilane, and thecorresponding mixtures.

[0028] The fluoro-alkyl functional organosilanes can be used directly asan additive in the present invention. Alternatively, the organosilanesmay be polymerized through the reactive alkoxysilyl functionality toafford fluoro-alkyl functional oligo- and polysiloxanes, which can beused as an effective additive in the present invention.

[0029] The compositions of the invention may optionally contain at leastone of fatty acid ester, fatty acid amide, anionic surfactant, or amixture containing at least one of the foregoing effective to reducefood deposit adhesion on articles and cookware made from thecomposition.

[0030] The optional fatty acid esters and fatty acid amides arederivatives of saturated and unsaturated normal fatty acids having fromabout fourteen to about thirty-six carbon atoms, inclusive.Representative fatty acids are, for example, tetradecanoic,pentadecanoic, hexadecanoic, heptadecanoic, octadecanoic, nonadecanoic,eicosanoic, henecosanoic, decosanoic, tricosanoic, tetracosanoic,pentacosanoic, hexacosanoic, triacontanoic, hentriacontanoic,dotriacontanoic, tetratriacontanoic, pentatriacontanoic,hexatriacontanoic acids, myristic, palmitic, stearic, arachidic, behenicand hexatrieisocontanoic (C₃₆) acids, palmitoleic, oleic, linolenic andcetoleic, and the like.

[0031] The methods of preparation of fatty acid esters and fatty acidamides employed are generally known in the art. For example, fatty acidesters are commonly prepared by the reaction of an alcohol and a fattyacid or a fatty acid derivative, such as a fatty acid halide. Polyolsare also useful to prepare fatty acid polyesters, as are thecorresponding polyamines to prepare fatty acid polyamides.Representative polyols are ethylene glycol, 1,3-propanediol,1,4-butanediol, 1,5-pentanediol 1,6-hexanediol, a polyglycol such asdiethylene glycol, triethylene glycol, dipropylene glycol, dibutyleneglycol, trimethylene glycol, isobutylene-ethylene glycol, trimethyleneglycol; the monoethyl, monopropyl or monobutyl ethers of glycerol,dicyclopentadienyl dimethanol, pentaerythritol, dipentaerythritol,tripentaerythritol, trimethylolpropane, trimethylolethane, etc.,glycerol, glycerol mono-acetate, mannitol, sorbitol, xylose, and thelike, or mixtures thereof.

[0032] In one embodiment of the invention, the optional fatty amides arepreferred as a food release additive in combination with at least onefluorinated compound. Included as additives are saturated fatty acidmonoamide (preferably, lauramide, palmitamide, behenamide, 1,2-hydroxystearamide); unsaturated fatty acid monoamide (preferably, oleamide,erucamide, recinoleamide); and N-substituted fatty acid amide (morepreferably, N-stearyl stearamide, N-behenyl behenamide, N-stearylbehenamide, N-behenyl stearamide, N-oleyl oleamide, N-oleyl stearamide,N-stearyl oleamide, N-stearyl erucamide, N-oleyl palmitamide; methylolamide (more preferably, methylol stearamide, methylol behenamide);saturated fatty acid bis-amide (more preferably, methylenebis-stearamide, ethylene bis-stearamide, ethylene bis-isostearamide,ethylene bis-hydroxystearamide, ethylene bis-behenamide, hexamethylenebis-stearamide, hexamethylene bis-behenamide, hexamethylenebis-hydroxystearamide, N,N′-distearyl adipamide, N,N′-distearylsebacamide); unsaturated fatty acid bis-amide (more preferably, ethylenebis-oleamide, hexamethylene bis-oleamide, N,N′-dioleyl adipamide,N,N′-dioleyl sebacamide; saturated or unsaturated fatty acid tetraamide, stearyl erucamide, ethylene bis stearamide and ethylene bisoleamide.

[0033] A large number of useful fatty amides are commercially availablefrom Humko Chemical Company, Memphis, Tenn. under the Kemamide tradenameand include, for example, Kemamide B (behenamide/arachidamide), KemamideW40 (N,N′-ethylenebisstearamide), Kemamide P181 (oleyl palmitamide),Kemamide S (stearamide), Kemamide U (oleamide), Kemamide E (erucamide),Kemamide O (oleamide), Kemamide W45 (N,N′-ethylenebisstearamide),Kemamide W20 (N,N′-ethylenebisoleamide), Kemamide E180 (stearylerucamide), Kemamide E221 (erucyl erucamide), Kemamide S180 (stearylstearamide), Kemamide S221 (erucyl stearamide), and the like. Inaddition, useful fatty amides are commercially available from CrodaUniversal Ltd., Hull East Yorkshire, England, under the Crodamidetradename and include, for example, Crodamide OR (oleamide), CrodamideER (erucamide), Crodamide SR (stearamide), Crodamide BR (behenamide),Crodamide 203 (oleyl palmitamide), Crodamide 212 (stearyl erucamide),and the like.

[0034] Another optional group useful as food release additives with theat least one fluorinated compound are the phosphonium sulfonatesillustrated by the general formula (XI) below:

[0035] wherein A is an alkyl group with 1-36 carbon atoms, alkenyl groupwith 4-24 carbon atoms, phenyl group, phenyl group substituted by alkylgroup with 1-18 carbon atoms, naphthyl group or naphthyl groupsubstituted by alkyl group with 1-18 carbon atoms, R¹, R² and R³ areidentical, each being an aliphatic hydrocarbon group with 1-8 carbonatoms or aromatic hydrocarbon group, and R⁴ is a hydrocarbon group with1-18 carbon atoms.

[0036] Phosphonium sulfonate shown by (XI) is composed of an organicsulfonate anion and an organic phosphonium cation. Examples of suchorganic sulfonate anion include aliphatic sulfonates such as methylsulfonate, ethyl sulfonate, propyl sulfonate, butyl sulfonate, octylsulfonate, lauryl sulfonate, myristyl sulfonate, hexadecyl sulfonate,2-ethylhexyl sulfonate, docosyl sulfonate and tetracosyl sulfonate andtheir mixtures, substituted phenyl sulfonates such as p-tosylate,butylphenyl sulfonate, dodecylphenyl sulfonate, octadecylphenylsulfonate, and dibutylphenyl, sulfonate, and substituted orunsubstituted naphthyl sulfonates such as naphthyl sulfonate,diisopropyl naphthyl sulfonate and dibutyinaphthyl sulfonate. Examplesof aforementioned phosphonium cation include aliphatic phosphonium suchas tetramethyl phosphonium, tetraethylphosophonium, tetrabutylphosphonium, triethylmethyl phosphonium, tributylmethyl phosphonium,tributylethyl phosphonium, trioctylmethyl phosphonium, trimethylbutylphosphonium, trimethyloctyl phosphonium, trimethyllauryl phosphonium,trimethylstearyl phosphonium, triethyloctyl phosphonium andtributyloctyl phosphonium and aromatic phosphoniums such as tetraphenylphosphonium, triphenylmethyl phosphonium, triphenylbenzyl phosphonium,and tributylbenzyl phosphonium.

[0037] Phosphonium sulfonates of the present invention can be obtainedby any combination of any of these organic sulfonate anions and organicphosphonium cations but this invention is not limited by the examplesgiven above. Phosphonium sulfonate of the present invention can beproduced by mixing metal salt of corresponding organic sulfonate andquaternary phosphonium salt in a solvent and washing out the byproductinorganic salt with water or extracting the product with an organicsolvent such as methanol, isopropanol or acetone.

[0038] Also useful are the ammonium sulfonate analogues of thephosphonium sulfonates. In these additives, the quaternary phosphoniumsalt is replaced by an ammonium salt. In certain embodiments of thepresent invention, preferred ammonium salts include monoethanolamine,triethanolamine, and lower alkylammonium salts including those havingfrom three to about ten carbon atoms such as isopropyl ammonium,tetramethyl ammonium, and tetrabutyl ammonium salts.

[0039] An effective food-releasing amount of the additive (or additives)is employed in the thermoplastic composition. Any amount of additivethat reduces the amount of food adhesion to obtain an acceptablecleanliness after washing is an effective food releasing amount providedthat the physical properties are substantially maintained or improved inthe final composition as compared to the composition not containing theadditive. In general, an effective amount of the additives ranges fromabout 0.1 to about 5.0 weight percent, preferably about 0.1 to about 4.0weight percent, based on the total weight of the composition. An actualamount depends on many factors, including the effectiveness of theparticular additive as a food releasing agent and the degree of foodrelease desired.

[0040] Compositions of the present invention can also include effectiveamounts of at least one additive selected from the group consisting ofanti-oxidants, flame retardants, drip retardants, crystallizationnucleators, dyes, pigments, colorants, reinforcing agents, fillers,stabilizers, antistatic agents, plasticizers and lubricants to changethe properties/characteristics of the composition. These additives areknown in the art, as are their effective levels and methods ofincorporation. Effective amounts of the additives vary widely, but theyare usually present in an amount up to about 50% or more by weight,based on the weight of the entire composition.

[0041] Mineral fillers are utilized in one embodiment of the invention.Useful mineral fillers include clays, talcs, micas, barium sulfate,titanium dioxide, wollastonites, zinc oxides, and the like. Anespecially preferred mineral filler is titanium dioxide. When used, theamount of mineral filler is generally up to about 50% by weight based onthe weight of the entire composition.

[0042] Preparation of the compositions of the present invention isnormally achieved by melt blending the ingredients under conditions forthe formation of an intimate blend. Such conditions often include mixingin single or twin screw type extruders or similar mixing devices thatcan apply a shear to the components. It is often advantageous to apply avacuum to the melt through a vent port in the extruder to removevolatile impurities in the composition.

[0043] All of the ingredients may be added initially to the processingsystem, or else certain additives may be pre-compounded with each other.It appears that certain properties, such as impact strength andelongation, are sometimes enhanced by initially pre-dispersing anyfillers with a portion of the resin to make a concentrate andsubsequently letting down the concentrate with additional resin and anyadditional ingredients. While separate extruders may be used, thesecompositions may also be prepared by using a single extruder havingmultiple feed ports along its length to accommodate the addition of thevarious components. It is also sometimes advantageous to employ at leastone vent port in each section between the feed ports to allow venting(either atmospheric or vacuum) of the melt. Those of ordinary skill inthe art will be able to adjust blending times and temperatures, as wellas component addition location and sequence, without undue additionalexperimentation.

[0044] The compositions of the present invention are useful for makingmolded articles such as cooking utensils and baking trays and pans aswell as various other molded articles. It should be clear that thepresent invention affords a method to reduce food adhesion to moldedarticles as well as a method to provide easier cleaning of moldedarticles.

[0045] All references cited herein are hereby incorporated in theirentireties.

[0046] The following examples are provided to illustrate the processaccording to the present invention. It should be understood that theexamples are given for the purpose of illustration and do not limit theinvention.

EXAMPLES

[0047] Example 1

[0048] A typical example of the claimed composition comprises 88.4% byweight of polyetherimide resin (Ultem® 1010-1000 resin available from GEPlastics, Vicat softening point of 215° C.), 10.7% by weight of TiO₂ and0.9% by weight of poly (tetrafluoroethylene), PTFE. The particular PTFEgrade used in this Example is Zonyl MP-1600 obtained from Du Pont deNemours Int'l SA, Geneva, Switzerland.

[0049] A dry-mixture of polyetherimide resin and PTFE is fed,simultaneously with TiO₂ powder, to the throat of a 25 mm twin screwextruder operated at 300 rpm and 360° C. The resulting material ispelletized, dried and Dynatup disks are injection molded using a 130 tonStork injection molding unit at melt temperature 360° C., injectionpressure 80 bar and mold temperature 160° C.

[0050] The adhesion to food deposits of the above blend formulation wasdetermined according to the following procedure: The Dynatup disks werewetted with a starch solution (Roux Blanc), dried and heated at 180° C.in air for 20 min. The soiled disks were washed for ca. 2 min at 65° C.in a Hobart multitank dishwasher using a 3 g/100 ml Divojet (alkaline)detergent solution. The washed samples were stained with potassiumiodide solution to detect the presence of carbohydrate residues on thesubstrate. All tests were done in duplo, i.e. using two disks of a givenformulation. Each sample was subjected to the described treatment fivetimes and the cleanliness of the sample surface was rated visually aftereach test. The average performance (i.e., surface cleanliness afterwashing) for each formulation was rated according to the followingscale: 1=very bad; 2=poor; 3=reasonable; 4=good. The described test wasperformed at DiverseyLever, Maarssenbroeksedijk 2, P.O. Box 10, 3600 AAMaarssen, The Netherlands.

[0051] Mechanical, impact and heat properties of injection molded testbars were tested according to standard ISO procedures. Results are givenin Table 1.

[0052] Example 2

[0053] As Example 1, with a composition comprising 89.1% by weight ofpolyetherimide resin (Ultem® 1010-1000 resin), 10.7% by weight of TiO₂and 0.2% by weight of an olefinic fluorocopolymer comprisingtetrafluoroethylene, hexafluoropropylene and vinylidene-fluoridemonomers.

[0054] Example 3

[0055] As Example 1, with a composition comprising 88.4% by weight ofpolyetherimide resin (Ultem® 1010-1000 resin), 10.7% by weight of TiO₂and 0.9% by weight of a olefinic fluorocopolymer comprisingtetrafluoroethylene, hexafluoropropylene and vinylidene-fluoridemonomers.

[0056] Example 4

[0057] As Example 1, with a composition comprising 88.8% by weight ofpolyetherimide resin (Ultem® 1010-1000 resin), 10.7% by weight of TiO₂and 0.5% by weight of a fluoroalkyl-trialkoxysilane, viz.3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyltriethoxysilane (DynasylanF8261 from Sivento Chemie Rheinfelden GmbH).

[0058] Example 5

[0059] As Example 1, with a composition comprising 84.8% by weight ofpolyetherimide resin (Ultem® 1010-1000 resin), 10.7% by weight of TiO₂and 4.5% by weight of poly(tetrafluoroethylene) (Zonyl MP-1600). ThisExample is included to show that fluoro-additives lose theireffectiveness as non-sticking agent in food release applications whenthe concentration of additive exceeds 4% by weight.

[0060] Other examples may include thermoplastic resins with a Vicatsoftening point above 180° C., such as: polyimides, polyamideimides,polysulfones such as polyarylsulfones, including polyphenylsulfones,polyethersulfones, polyetherketones, polyetheretherketones, aromaticcopolyesters, and the like. TABLE 1 Properties of thermoplasticcompositions described in the Examples. China ware Reference 1 Reference2 Example 1 Example 2 Example 3 Example 4 Example 5 Ultem 1010 resin N/A100% 89.3% 88.4% 89.1% 88.4% 88.8% 84.8% Inorg. Filler N/A N/A 10.7%TiO₂ 10.7% TiO₂ 10.7% TiO₂ 10.7% TiO₂ 10.7% TiO2 10.7% TiO₂ FluorinatedN/A N/A N/A 0.9% PTFE 0.2% fluoro- 0.9% fluoro- 0.5% 4.5% PTFE Compoundcopolymer copolymer fluoroalkyl- trialkoxysilane Food Adhesion 1 (verybad) 1 (very bad) 1 (very bad) 4 (good) 3 (reasonable) 3 (reasonable) 3(reasonable) 1 (very bad) Rating E-Modulus (Mpa) 3225 3458 3597 36073609 3602 3342 Yield Stress (Mpa) 111 111 111 110 110 111 107 YieldStrain (%) 7.0 6.5 5.7 5.6 5.6 5.7 6.6 INI (kJ/m2) 4.4 4.6 5.1 5.0 5.15.1 5.2 Vicat (° C.) 214 216 213 212 212 213 215

[0061] As can be noted by the data in Table 1, reduced food depositadhesion on articles was achieved with the compositions of theinvention. This result was unexpected based on the prior art forreducing food deposit adhesion on articles.

[0062] The preceding examples are set forth to illustrate specificembodiments of the invention and are not intended to limit its scope. Itshould be clear that the present invention includes articles from thecompositions as described herein. Additional embodiments and advantageswithin the scope of the claimed invention will be apparent to one ofordinary skill in the art.

1. A resin composition comprising: a) a polysulfone or polyethersulfoneresin with a glass transition temperature of at least 180° C.; b) afluorinated polyolefin in an amount up to about 4% by weight effectiveto reduce food deposit adhesion on cookware made from the composition;and c) an anionic surfactant.
 2. The composition of claim 1, comprisingthe polysulfone resin.
 3. The composition of claim 2, wherein thepolysulfone resin comprises repeating units of the formula


4. The composition of claim 1, comprising the polyethersulfone resin. 5.The composition of claim 4, wherein the polyethersulfone resin comprisesrepeating units having the formula


6. The composition of claim 1, wherein the fluorinated polyolefin is apolymer of a perfluorinated monoolefin or a partially fluorinatedmonoolefin.
 7. The composition of claim 1, wherein the fluorinatedpolyolefin is a polymer of one or more fluorinated monomers containingethylenic unsaturation and optionally, one or more other compoundscontaining ethylenic unsaturation.
 8. The composition of claim 1,wherein the fluorinated polyolefin is at least one of poly(vinylfluoride), poly(vinylidene fluoride), polytrifluoroethylene,polychlorotrifluoroethylene, polybromotrifluoroethylene,polytetrafluoroethylene, or copolymers thereof.
 9. The composition ofclaim 1, wherein the fluorinated polyolefin is a copolymer oftetrafluoroethylene and hexafluoropropylene.
 10. The composition ofclaim 1, wherein the fluorinated polyolefin is a fluorinatedpolyethylene comprising repeating units of the structural formula:

wherein b is an integer in excess of 50 and Y¹ to Y⁴, which may be thesame or different, are selected from the group consisting of hydrogen,chlorine, bromine and fluorine, with the proviso that at least one of Y¹to Y⁴ is fluorine.
 11. The composition of claim 1, comprising about 0.1%to about 4% by weight of the fluorinated polyolefin.
 12. The compositionof claim 1, wherein the anionic surfactant is a phosphonium sulfonatehaving the formula

wherein A is an alkyl group with 1-36 carbon atoms, alkenyl group with4-24 carbon atoms, phenyl group, phenyl group substituted by alkyl groupwith 1-18 carbon atoms, naphthyl group or naphthyl group substituted byalkyl group with 1-18 carbon atoms; R¹, R², and R³ are identical, eachbeing an aliphatic hydrocarbon group with 1-8 carbon atoms or aromatichydrocarbon group, and R⁴ is a hydrocarbon group with 1-18 carbon atoms.13. The composition of claim 12, wherein the phosphonium sulfonatecomprises a sulfonate anion selected from the group consisting of methylsulfonate, ethyl sulfonate, propyl sulfonate, butyl sulfonate, octylsulfonate, lauryl sulfonate, myristyl sulfonate, hexadecyl sulfonate,2-ethylhexyl sulfonate, docosyl sulfonate, tetracosyl sulfonate,p-tosylate, butylphenyl sulfonate, dodecylphenyl sulfonate,octadecylphenyl sulfonate, dibutylphenyl sulfonate, naphthyl sulfonate,diisopropyl naphthyl sulfonate, and dibutylnaphthyl sulfonate.
 14. Thecomposition of claim 12, wherein the phosphonium sulfonate comprises aphosphonium cation selected from the group consisting oftetramethylphosphonium, tetraethylphosophonium, tetrabutylphosphonium,triethylmethylphosphonium, tributylmethylphosphonium,tributylethylphosphonium, trioctylmethy phosphonium,trimethylbutylphosphonium, trimethyloctylphosphonium,trimethyllaurylphosphonium, trimethylstearylphosphonium,triethyloctylphosphonium, tributyloctylphosphonium,tetraphenylphosphonium, triphenylmethylphosphonium,triphenylbenzylphosphonium, and tributylbenzylphosphonium.
 15. Thecomposition of claim 1, wherein the anionic surfactant comprises anammonium sulfonate.
 16. The composition of claim 15, wherein theammonium sulfonate comprises a sulfonate anion selected from the groupconsisting of methyl sulfonate, ethyl sulfonate, propyl sulfonate, butylsulfonate, octyl sulfonate, lauryl sulfonate, myristyl sulfonate,hexadecyl sulfonate, 2-ethylhexyl sulfonate, docosyl sulfonate,tetracosyl sulfonate, p-tosylate, butylphenyl sulfonate, dodecylphenylsulfonate, octadecylphenyl sulfonate, dibutylphenyl sulfonate, naphthylsulfonate, diisopropyl naphthyl sulfonate, and dibutyinaphthylsulfonate.
 17. The composition of claim 15, wherein the ammoniumsulfonate comprises an ammonium cation selected from the groupconsisting of tetramethylammonium, tetraethylammonium,tetrabutylammonium, triethylmethylammonium, tributylmethylammonium,tributylethylammonium, trioctylmethylammonium, trimethylbutylammonium,trimethyloctylammonium, trimethyllaurylammonium,trimethylstearylammonium, triethyloctylammonium, tributyloctylammonium,tetraphenylammonium, triphenylmethylammonium, triphenylbenzylammonium,tributylbenzylammonium, monoethanolammonium, and triethanolammonium, andisopropylammonium.
 18. The composition of claim 1, comprising about 0.1to about 5% by weight of the anionic surfactant.
 19. The composition ofclaim 1, further comprising a resin selected from the group consistingof polycarbonates, polyimides, polyetherimides, polyamides,polyamideimides, polyetherketones, aromatic copolyesters, and blends ofthe foregoing resins.
 20. The composition of claim 1, further comprisingat least one fluorinated siloxane or fluorinated polysiloxane.
 21. Thecomposition of claim 1, further comprising a mineral filler selectedfrom the group consisting of clays, talcs, micas, barium sulfates,titanium dioxides, wollastonites, and zinc oxides.
 22. The compositionof claim 1, further comprising a food release additive selected from thegroup consisting of fatty acid esters, fatty acid amides, and mixturesthereof.
 23. The composition of claim 1 further comprising at least oneadditive selected from the group consisting of anti-oxidants, flameretardants, drip retardants, crystallization nucleators, dyes, pigments,colorants, reinforcing agents, fillers, stabilizers, antistatic agents,plasticizers, and lubricants.
 24. A resin composition consistingessentially of: a polysulfone or polyethersulfone resin with a glasstransition temperature of at least 180° C.; about 0.1 to about 4% byweight of a fluorinated polyolefin; and about 0.1% to about 5% by weightof an anionic surfactant.
 25. A resin composition consisting essentiallyof: a polysulfone or polyethersulfone resin with a glass transitiontemperature of at least 180° C.; about 0.1 to about 4% by weight of afluorinated polyolefin; about 0.1% to about 5% by weight of an anionicsurfactant; and up to 50% by weight of a mineral filler.
 26. An articlecomprising the composition of claim 1.